Electron Transfer Kinetics of a Series of Copper Complexes with Tripodal Tetradentate Guanidine Quinolinyl Ligands

Abstract

Copper complexes of tripodal ligands have been used as model systems for electron transfer proteins for decades, displaying a broad range of electron self-exchage rates. We herein report a group of six tripodal tetradentate triarylamine ligands which display a varying number of guaninidine and 2-methylquinolinyl moierties. Their corresponding Cu(I) complexes have been (re)synthesized and studied with regard to their electron transfer properties. While their solid state structures are four-coordinate and display an uncommon umbrella distortion, DFT studies of the Cu(II) systems reveal that they gain an additional ligand in form of a solvent molecule and exhibit a range of possible conformers that likely co-exist in thermal equilibrium. The redox-couples’ electron self-exchange rates were analyzed using Marcus theory and vary over four orders of magnitdue which cyclic voltammetry studies suggest to be due to a gated addition-oxidation electron transfer mechanism. This mechanism deviates from previously studied systems, likely due to the structural anomalies of the Cu(I) systems. This demonstrates that the chosen path of tripodal model systems can be influenced by molecular design.